N-({60 -thiocyanoacetyl)indolines

ABSTRACT

New chemical compositions of the formula   WHEREIN EACH R is selected from the group consisting of hydrogen and alkyl; A forms a substituted or unsubstituted hydrocarbon ring of six carbon atoms wherein the substituents are selected from the group consisting of alkyl, alkenyl, halogen, haloalkyl, alkoxy, nitro, and dialkylamino; m is an integer from 1 to 3; n is an integer from 0 to 1; and m + n is an integer from 2 to 3. A fungicidal composition comprising an inert carrier and, as an essential active ingredient, in a quantity toxic to fungi, a compound of the above description. A method for the control of fungi which comprises applying to said fungi a fungicidal composition comprising an inert carrier and, in a quantity toxic to fungi a compound heretofore described.

[ Dec. 30, 1975 N-(a-THIOCYANOACETYL)INDOLINES Inventors: Sidney B.Richter, Chicago; Alfred A. Levin, Skokie, both of ill.

[73] Assignee: Velsicol Chemical Corporation,

. Chicago, ill.

[22] Filed: Apr. 5, 1974 [21] Appl. No.: 461,076

Related U.S. Application Data Division of Ser. No. 284,295, Aug. 28,1972, Pat. No. 3,869,471, which is a division of Ser, No. 165,348, July22, 1971, Pat. No. 3,723,439, which is a continuation-in-part of Ser.No. 732,822, May 29, 1968, abandoned.

OTHER PUBLICATIONS Shikhiev et al., Chem. Abstracts, Vol. 78, p. 472,No. 293940 (1973)..

Primary Examiner-Lewis Gotts Assistant Examiner-S. P. Williams Attorney,Agent, or FirmRobert J. Schwarz; Dietmar H. Olesch [57] ABSTRACT Newchemical compositions of the formula CR a)m\ N C CHzSC wherein each R isselected from the group consisting of hydrogen and alkyl; A forms asubstituted or unsubstituted hydrocarbon ring of six carbon atomswherein the substituents are selected from the group consisting ofalkyl, alkenyl, halogen, haloalkyl, alkoxy, nitro, and dialkylamino; mis an integer from 1 to 3; n is an integer from 0 to l; and m n is aninteger from 2 to 3. A fungicidal composition comprising an inertcarrier and, as an essential active ingredient, in a quantity toxic tofungi, a compound of the above description. A method for the control offungi which comprises applying to said fungi a fungicidal compositioncomprising an inert carrier and, in a quantity toxic to fungi a compoundheretofore described.

2 Claims, No Drawings N-( a-THIOCYANOACETYL)INDOLINES dialkylamino; m isan integer from 1 to 3; n is an integer This is a division ofapplication Ser. No. 284,295 filed from 0 to and m n is an integer from2 o 3. Aug, 28, 1972, no U S P t, No, 3,869,471 hi h i a In a preferredembodiment of this invention each R is division of application Ser. No.165,348 filed July 22, 5 Select! frOm th group C sisting Of hydrogen and1971, now U S Pat, No, 3,723,439, whi h i a lower alkyl; A forms asubstituted or unsubstituted tinuation-in-part of Ser. No. 732,822 filedMay 29, hydrocarbon ring having a maximum of four substitu- 1968, nowabandoned. ents wherein the substituents are selected from the Thisinvention relates to new chemical compositions group consisting of loweralkyl, lower alkenyl, chlorine, of matter. More particularly thisinvention relates to 10 bromine, lower chloroalkyl, lower bromoalkyl andnew pesticidally-active heterocyclic compounds of the lower fluoroalkyl,lower alkoxy, nitro and di(lower formula alkyl) amino. The term lower,as used herein, desig- N c CH2SCN wherein each R is selected from thegroup consisting of nates a straight or branched carbon chain containinga hydrogen and alkyl; A forms a substituted or unsubsti- 25 maximum of 5carbon atoms.

tuted hydrocarbon ring of six carbon atoms wherein the Exemplary 0f C mPLmd Within the cop f the ubStituents are selected from the groupConsisting of present invention which are of particular interest arealkyl, alkenyl, halogen, haloalkyl, alkoxy, nitro and compounds havingthe following structural formulas:

a X2 l R2 B x [mm-(m son (II)- wherein X X X and X are independentlyselected from the group consisting of hydrogen, alkyl, alkenyl, halogen,haloalkyl, alkoxy, nitro and dialkylamino, and R is as heretoforedescribed.

The compounds of the present invention are unexpectedly useful aspesticides and particularly as fungicides.

The new compounds of the present invention can be prepared fromcompounds having the following formula 1 wherein R, A, m and n are asheretofore described, by

reaction with sodium thiocyanate or potassium thiocyanate. This reactioncan be readily effected by combining a compound of Formula VI with adescribed thiocyanate in an inert organic solvent such as ethanol. Thisreaction usually requires heating and often reflux temperatures of thereaction mixtures are desirable. To recover the desired product aftercompletion of the reaction, the reaction mixture can be first filteredto remove any inorganic salts which have formed and then stripped ofsolvent by evaporation, distillation or the like. The resulting productcan be used as such or can be further purified if desired by washing,triturating, crystallization and the like if the product is a solid orif the product is a liquid by extraction, distillation, chromatographyor other common techniques employed in the art.

H C CH Cl Exemplary of the compound of Formula VI which are suitable forpreparing the new compounds of the present invention arel-(a-chloroacetyl)indoline,2-(achloroacetyl)-isoindoline,2-(a-chloroacetyl)-l ,2,3 ,4- tetrahydroisoquinoline,2-(a-chloroacetyl)- l ,2,3 ,4-tetrahydroisoquinoline,l-(a-chloroacetyl)-4-chloroindoline,l-(a-chloroacetyl)-3-methylindoline, l-(achloroacetyl)-2-methyl-S-nitroindoline lachloroacetyl)-5-nitroindoline,l-(a-chloroacetyl )-7- bromo-S-nitroindoline,l-(a-chloroacetyl)-6-methoxyindoline,2-(a-chloroacetyl)-l-methylisoindoline, 2- (a-chloroacetyl) l -methyl-l,2,3 ,4-tetrahydroisoquinoline, l-(a-chloroacetyl )-6-methoxy-l ,2,3,4-tetrahydroquinoline, l-(a-chloroacetyl)-6,8-dimethyl-1,2,3 ,4-tetrahydroquinoline, 2-(a-chloroacetyl)-7-nitrol,2,3',4-tetrahydroisoquinoline, l-(a-chloroacetyl)- decahydroquinoline,l-(a-chloroacetyl)-3a,4,7,7a-tetrahydroindoline,1-(a-chloroacetyl)-2-methyl-hexahydroindoline and the like.

The compounds of Formula VI can be prepared from compounds of thefollowing formula wherein R, A, m and n are as heretofore described, byreaction with chloroacetyl chloride. This reaction can be readilyeffected by adding the chloroacetyl chloride to a solution of a compoundof Formula VII in a suitable inert organic solvent such as benzene. Inmany instances this reaction is exothermic and cooling of the reactionmixture or a slow controlled addition of the chloroacetyl chloride canbe desirable. The presence of an acid scavenger such as a tertiary inthe reaction medium is preferred in order to remove the hydrogenchloride which is formed. After the completion of the reaction thedesired product can be recovered by first filtering the reaction mixtureto remove any insolubles which have formed such as amine hydrochloridewhen a tertiary amine is used as an acid scavenger, and thereafterevaporating the solvent used. The remaining product can then be used assuch or can be further purified by distillation if a liquid or byrecrystallization if a solid.

Exemplary compounds of Formula VII suitable for preparing the compoundsof Formula V1 are indoline, isoindoline, 1,2,3,4-tetrahydroquinoline,1,2,3,4-tetrahydroisoquinoline, 4-chloroindoline, 3-methylindoline,2-methyl-5-nitroindoline, 7-bromo-5nitroindoline, 2,3-dimethylindoline,4-methoxyindoline, 6- methoxyindoline, 6-ethyl-2,B-dimethylindoline, 1-methylisoindoline, 1 -butylisoindoline, 1 -methyl- 1 ,2,3,4-tetrahydroisoquinoline, 5-methoxy-1,2,3 ,4-tetrahydroisoquinoline,3-methy1-1,2,3 ,4-tetrahydroquinoline,6-methyl-1,2,3,4-tetrahydroquinoline, 6,8-dimethyl-1,2 ,3,4-tetrahydroquinoline, 6-methoxy- 1 ,2,3 ,4-tetrahydroquinoline,7-nitro-1,2,3,4-tetrahydroisoquinoline, 1-methy1-5-nitro-1,2,3,4-tetrahydroisoquinoline, 4,5-dihydroindoline, 5,6-dihydroindoline,3a,4,7,7a-tetrahydroindoline, hexahydroindoline, 3a,4,7,7a-tetrahydroisoindoline, 3a,4,5 ,6-tetrahydroisoindoline,hexahydroisoindoline, 1,2,3,4,5,8-hexahydroisoquinoline, 1,2,3,4,5,6,7,8-octahydroisoquinoline, 1,2,3 ,4,5,8-hexahydro-6-methoxyisoquinoline, 1'-methy1decahydroisoquinoline,

1,2,3,4,4a,5 ,6,7-octahydroquinoline, 1,2,3,4,5,6,7,8-

octahydroquinoline and the like.

The manner in which the compounds of the present invention can beprepared readily is further illustrated in the following examples:

EXAMPLE l Preparation of 1-(a-Thiocyanoacetyl)Indolinel-(a-Chloroacetyl)indoline (19.6 grams; 0.1 mol), potassium thiocyanate(18 grams; 0.2 mol) and ethanol (100 ml.) were charged into a glassreaction flask equipped with stirrer and reflux condenser. The reactionmixture was heated at reflux for a period of about 4 hours. After thistime the mixture was cooled and filtered. The filtrate was evaporatedunder reduced pressure to yield a brown solid as a residue. The residuewas washed with water and dried. The dried product was thenrecrystallized from a benzene-pentane mixture to yield1-(a-thiocyanoacetyl)indoline having a melting point of 125 to 127 C.and having the following elemental analysis as calculated for C H N OS CH N S Theoretical 60.58 4.62 12.84 14.69 Found 61.07 4.64 12.71 14.32

EXAMPLE 2 Preparation of 2-(a-Chloroacetyl)lsoindoline over a period ofabout 20 minutes. The mixture is stirred for an additional period ofabout 30 minutes and is then filtered. The filtrate is then stripped ofbenzene to yield2-(a-ch1oroacetyl)isoindoline.

EXAMPLE 3 Preparation of 2-(a-Thiocyanoacetyl)-Isoindoline2-(a-Ch1oroacetyl)isoindoline (19.6 grams; 0.1 mol), potassiumthiocyanate 18 grams; 0.2 mol) and ethanol ml.) are charged into a glassreaction flask equipped with stirrer and reflux condenser. The reactionmixture is heated at reflux for a period of about 4 hours. After thistime the mixture is cooled and filtered.

The filtrate is stripped of solvent under reduced pressure and theresulting residue is washed with water, dried and is recrystallized toyield 2-(a-thiocyanoacetyl)isoindoline.

EXAMPLE 4 Preparation of 1 -(a-Ch1oroacety1)-1 ,2,3,4-tetrahydroquino1ine A solution of 1,2,3,4-tetrahydroquinoline (66.5grams; 0.5 mol) and triethylamine (50 grams) in benzene (1000 ml) wasplaced in a glass reaction flask equipped with mechanical stirrer andreflux condenser. Chloroacetyl chloride (56.5 grams; 0.5 mol) was slowlyadded with stirring over a period of about 15 minutes. An exotherm wasobserved. The mixture was then stirred for an additional period of about15 minutes, was cooled and then filtered. The filtered benzene solutionwas then stripped of solvent resulting in a dark colored oil. The oilwas distilled under reduced pressure to yieldl-(a-chloroacetyD-l,2,3,4-tetrahydroquinoline as a yellow oil having aboiling point of to 173 C. at 3.5 mm of Hg pressure and a refractiveindex of 1.5865 at 25 C.

EXAMPLE 5 Preparation of 1-(a-Thiocyanoacetyl)-1 ,2,3,4-tetrahydroquinoline 1 -(a-Chloroacety1)- 1 ,2,3,4-tetrahydroquinoline (20.9 grams; 0.1 mol), potassium thiocyanate (18grams; 0.2 mol) ethanol (100,ml.) and a few crystals of sodium iodidewere charged into a glass reaction vessel equipped with a mechanicalstirrer and reflux condenser. The reaction mixture was heated at refluxfor a period of about 7 hours. After this time the mixture was cooledand filtered. The filtrate was poured into cold water resulting in theformation of a white solid. The solid was dissolved in ether and theetheral solution dried over anhydrous magnesium sulfate and filtered.The dried solution was then stripped of ether to yield a yellow solid.The solid was dried in vacuo and recrystallized from ether to yield1-(a-thiocyanoacetyl)-1,2,3 ,4- tetahydroquinoline having a meltingpoint. of 73-74.5 C. and having the following elemental analysis ascalculated for c n n os EXAMPLE 6 Preparation of 2-(a-Chloroacetyl)-l,2,3,4-tetrahydroisoquinoline A solution of1,2,3,4-tetrahydroisoquinoline (66.5 grams; 0.5 mol) and triethylamine(50 grams; 0.5 mol) in benzene (1 l.) was charged into a glass reactionvessel equipped. with a stirrer, reflux condenser and addition funnel.Chloroacetyl chloride (56.5 grams; 0.5 mol) was slowly added over aperiod of about minutes. An exotherm was observed. Stirring wascontinued for an additional 15 minutes after which the reaction mixturewas cooled and filtered. The filtrate was stripped of benzene underreduced pressure resulting in a dark colored oil as a residue. The darkoil was distilled in vacuo to yield2-(a-chloroacetyl)-1,2,3,4-tetrahydroisoquinoline as a yellow oil havinga boiling point of 190 to 195 C. at 7 mm of Hg pressure, and an index ofrefraction at 27 C. of 1.5813.

EXAMPLE 7 Preparation of 2-(a-Thiocyanoacetyl)-l,2,3,4-tetrahydroisoquinoline 2-(a-Chloroacetyl)-1 ,2,3,4-tetrahydroisoquinoline (13 grams; 0.06 mol), potassium thiocyanate(11 grams), ethanol (100 ml.) and a few crystals of sodium iodide werecharged into a glass reaction flask equipped with stirrer and refluxcondenser. The reaction mixture was heated, with stirring, for a periodof about 2 hours. After this time the reaction mixture was cooled andfiltered. The filtrate was poured into 1600 ml. of cold water resultingin the formation of an oil. The oil solidified upon standing. The solidwas recovered by filtration and dissolved in ether. The etheral solutionwas dried over anhydrous magnesium sulfate, was filtered and evaporatedto yield a yellow solid. The solid was recrystallized from ether toyield 2(a-thiocyano)-1,2,3,4-tetrahydroisoquinoline having a meltingpoint of 73 to 74 C. and having the following elemental analysis ascalculated for C H N OS:

C H N S Theoretical 62.04 5.21 12.06 13.80 Found 61.56 5.11 12.00 13.20

EXAMPLE 8 Preparation of 1-(a-Chloroacetyl)-4-chloroindoline EXAMPLE 9Preparation of 1-(a-Thiocyanoacetyl)-4-chloroindoline1-(a-Chloroacetyl)-4-chloroindoline (23 grams; 0.1 mol) potassiumthiocyanate (18 grams; 0.2 mol), ethanol (100 ml.) and a few crystals ofsodium iodide are charged into a glass reaction flask equipped with amechancial stirrer and reflux condenser. The reaction mixture is heatedat reflux for a period of about 4 hours. After this time the reactionmixture is cooled and filtered. The filtrate is stripped of solventunder reduced pressure and the resulting residue is washed with water,dried and is recrystallized to yieldl-(a-thiocyanoacetyl)-4-chloroindoline.

EXAMPLE 10 Preparation of1-(a-Chloroacetyl)-6,8-dimethyl-1,2,3,4-tetrahydroquinoline A solutionof 6,8-dimethyl-l,2,3,4-tetrahydroquinoline (84 grams; 0.5 mol) andtriethylamine grams) in benzene (100 ml) is placed in a glass reactionflask equipped with stirrer, reflux condenser and addition funnel.Chloroacetyl chloride (56.5 grams; 0.5 mol) is slowly added, withstirring over a period of about 30 minutes. The mixture is stirred foran additional period of about 30 minutes and is then filtered. Thefiltrate is stripped of benzene to yield 1-(a-chloroacetyl)-6,8-dimethyl-l,2,3,4-tetrahydroquinoline as a residue.

EXAMPLE 1 1 Preparation of 1 -(a-Thiocyanoacetyl)-6,8-dimethyl-1 ,2,3,4-tetrahydroquinoline 1-(a-Chloroacetyl)-6,8-dimethyl-l,2,3,4-tetrahydroquinoline (24 grams; 0.1 mol), potassium thiocyanate(18 grams; 0.2 mol), ethanol (1000 ml.) and a few crystals of sodiumiodide are charged into a glass reaction flask equipped with amechanical stirrer and reflux condenser. The reaction mixture is heatedat reflux for a period of about 5 hours. After this time the reactionmixture is cooled and filtered. The filtrate is stripped of solvent andthe resulting residue is washed with water and is then recrystallized toyield l-(a-thiocyanoacetyl )-6,8-dimethyll ,2,3 ,4-tetrahydroquinoline.

EXAMPLE 12 Preparation of l-(a-Chloroacetyl) Decahydroquinoline Asolution of decahydroquinoline (21 grams; 0.15 mol) and a triethylamine(15 grams) in benzene (250 ml.) was charged into a 500 ml glass reactionflask equipped with mechanical stirrer, reflux condenser and additionfunnel. Chloroacetyl chloride (18 grams; 0.15 mol) was slowly added,with stirring, over a period of about 10 minutes. After the addition wascompleted stirring was continued for a period of about 15 minutes. Afterthis time the reaction mixture was filtered to remove the triethylaminehydrochloride which had formed. The filtered solution was then washedtwice with 250 ml portions of dilute hydrochloric acid and then withwater, and thereafter dried over anhydrous magnesium sulfate. The driedsolution was filtered and stripped of benzene under reduced pressure toyield an oil. The oil was distilled twice under reduced pressure toyield l-(a-chloroacetyl) decahydroquinoline as a yellow oil having aboiling point of 143 to 146 C. at 0.3 mm Hg pressure, a refractive indexof 1.5212 at 25 C. and having the following elemental analysis ascalculated.for C l-l ClNO:

. C H C1 N Theoretical, 61.24 8.41 16.44 6.49 Found, 60.95 8.46 16.496.48

EXAMPLE 13 Preparation of l-(a-Thiocyanoacetyl) Decahydroquinolinel-(a-Chloroac'etyl) decahydroquinoline grams; 0.023 mol), potassiumthiocyanate (4.2 grams; 0.05 mol) and ethanol (50 ml) were charged intoa glass reaction flask equipped with mechanical stirrer and refluxcondenser. The reaction mixture was stirred at reflux, with stirring,for a period of about 2'hours. After this time, the reaction mixture wascooled, filtered and poured into a large volume of cold water to yieldan oil. The oil was extracted with ether and the etheral solution waswashed with water'and dried over anhydrous magnesium sulfate. The driedsolution was filtered and stripped of solvent on a steam bath to yield adark oil.- The oil was allowed to stand whereupon it solidified. Thesolid was then ground and dried in vacuo to yield 2.8 grams of product.The product was recrystallized from hexane and was dried in anAbderholden Apparatus to yield l-(a-thiocyanoacety1).decahydroquinolinehaving a melting point of 200 to 202 C. and having the followingelemental analysis as calculated for C H N OS:

C H N S Theoretical, 60.46 7.61 11.76 13.45 Found, 61.14 7.98 11.8713.21

EXAMPLE 14 3-Methylindolene chloroacetyl chloride potassium thiocyanatel-(a-thiocyanoacetyl)-3-methy1indolene.

EXAMPLE 15 2-Methyl-5-nitroindolene chloroacetyl chloride potassiumthiocyanate l-(a-thiocyanoacetyllZ- methyl-S-nitroindolene. I

EXAMPLE 16 4-Methoxyindolene chloroacetyl chloride potassium thiocyanatel-(a-thiocyanoacetyl)-4-methoxyindolene.

EXAMPLE 17 l-Methyl-l ,2,3,4-tetrahydroisoquinoline chloroacetylchloride potassium thiocyanate Z-(a-thiocyanoacetyl)-l-methyl-l,2,3,4-tetrahydroisoquinoline.

EXAMPLE 18 6-Methoxy-l ,2,3,4-tetrahydroquinoline chloroacetyl chloridepotassium thiocyanate -1-(a-thiocyanoacety1)-6-methoxyl ,2,3,4-tetrahydroquinoline.

EXAMPLE 19 7-Nitro-l,2,3,4-tetrahydroisoquinoline chloroacetyl chloridepotassium thiocyanate 2-(a-thiocyanoacetyl)-7-nitro-l,2,3,4-tetrahyclroisoquinoline.

EXAMPLE 20 4,5-Dihydroindoline chloroacetyl chloride potassiumthiocyanate l-(a-thiocyanoacetyl)-4,5-dihydroindoline.

EXAMPLE 21 3a,4,7,7a-Tetrahydroindoline chloroacetyl chloride potassiumthiocyanate l-(a-thiocyanoacetyl)- 3a,4,7,7a-tetrahydroindoline.

EXAMPLE 22 Hexahydroisoindoline chloroacetyl chloride potassiumthiocyanate Z-(a-thiocyanoacetyl)hexahydroisoindoline.

EXAMPLE 23 1,2,3,4,4a,5,6,7-Octahydroquinoline chloroacetyl chloridepotassium thiocyanate l-(a-thiocyanoacetyl)-l ,2,3 ,4,4a,5,6,7-octahydroquinoline.

EXAMPLE 24 l,2,3,4,5,8-Hexahydroisoquinoline chloroacetyl chloridepotassium thiocyanate Z-(a-thiocyanoacetyl)-l ,2,3 ,4,5,8-hexahydroisoquinoline.

EXAMPLE 25 1 ,2,3,4,5 ,8-Hexahydro-6-meth0xyisoquinoline chloroacetylchloride potassium thiocyanate 2-(athiocyanoacetyl)-l ,2,3,4,5,8-hexahydro-6-methoxyisoquinoline.

EXAMPLE 26 1 ,2,3 ,4-Tetrahydro-6-dimethylaminoquinoline chloroacetylchloride potassium thiocyanate l-(athiocyanoacetyl )-l ,2,3,4-tetrahydro-6-dimethylaminoquinoline.

The new compounds of this invention are fungicidal in their ability tokill, inhibit, or inactivate a fungus so that it does not grow.Practically, these compounds can be used to prevent fungi and molds fromharming cloth, wood, plants, seeds, fruit, animals, or whatever elsethey attack. The fungicidal compounds should preferably be appliedbefore the infection has occurred and certainly before ithas progressedvery far.

For practical use as fungicides, the compounds of this invention aregenerally incorporated into fungicidal compositions which comprise aninert carrier and a fungicidally toxic amount of such a compound. Suchfungicidal compositions, which are usually known in the art asformulations, enable the active compound to be applied conveniently tothe site of the fungus infestation in any desired quantity. Thesecompositions can be solids such as dusts, granules, or wettable powders,or they can be liquids such as solutions, aerosols, or emulsifiableconcentrates.

For example, dusts can be prepared by grinding and blending the activecompound with a solid inert carrier such as'th'e talcs, clays, silicas,pyrophyllite, and the like.,Granular formulations can be prepared byimpregnating the compound, usually dissolved in a suitable solvent, onto and into granulated carriers such as the attapulgites or thevermiculities, usually of a particle size range of from about 0.3 to 1.5mm. Wettable powders, which can be dispersed in water to any desiredconcentration of the active compound, can be prepared by incorporatingwetting agents into concentrated dust compositions.

In some cases the active compounds are sufficiently soluble in commonorganic solvents such as kerosene or xylene so that they can be useddirectly as solutions in these solvents. Frequently, solutions offungicides can be dispersed under superatmospheric pressure as aerosols.However, preferred liquid fungicidal compositions are emulsiflableconcentrates, which comprise an active compound according to thisinvention and as the inert carrier, a solvent and an emulsifier. Suchemulsifiable concentrates can be diluted with water to any desiredconcentration of active compound for application as sprays to the siteof the fungus infestation. The emulsifiers most commonly used in theseconcentrates are nonionic or mixtures of nonionic with anionicsurface-active agents.

A typical fungicidal composition according to this invention isillustrated by the following example, in which the qualities are inparts by weight.

EXAMPLE 27 Preparation of a Dust The above ingredients are mixed in amechanical grinder-blender and are ground until a homogeneous,free-flowing dust of the desired particle size is obtained. This dust issuitable for direct application to the site of the fungus infestation.

The fungicides of this invention can be applied in any manner recognizedby the art. The concentration of the new compounds of this invention inthe fungicidal compositions will very greatly with the type offormulation and the purpose for which itis designed, but generally thefungicidal compositions will comprise from about 0.05 to about 95percent by weight of the active compounds of this invention. In apreferred embodiment of this invention, the fungicidal compositions willcomprise from about 5 to about 75 percent by weight of the activecompound. The compositions can also comprise such additional substancesas other pesticides, spreaders, adhesives, stickers, fertilizers,activators, synergists, and the like.

The compounds of the present invention are also useful when combinedwith other fungicides in the fungicidal compositions heretoforedescribed. The other fungicides can comprise from about 5 percent toabout 95 percent of the active ingredients in the fungicidalcompositions. Use of combinations of these other fungicides with thecompounds of the present invention provides fungicidal compositionswhich are more effective in controlling fungi and often provide resultsunattainable with separate compositions of the individual fungicides.The other fungicides, with which the compounds of this invention can beused in the fungicidal compositions to control fungi, can includefungicides such as 2-aminobutane, bordeaux mixture, ammonium dimethyldithiocarbamate, benzoyl trimethyl ammonium bromide, cadmium sulfate,captan, chloranil, copper sulfate, cycloheximide, dichlone,2,4-dichloro- 6-(2-chloroanilino)-s-triazine, DDT, dichloran,pdimethylaminobenzenediazo sodium sulfonate, dinocap, diphenylmercuriS-hydroxyquinolinate, dodine,

ethylmercuric chloride, ferbam, folpet, gliodin, maneb, metham, mezineb,nabam, pentachloronitrobenzene, PMA, phenylmercuric urea, streptomicin,thiram, zineb, ziram, difolatan, PCNB, and the like.

Such fungicides can also be used in the methods and compositions of thisinvention in the form of their esters, amides, and other derivativeswhenever applicable to the particular parent compound.

When the compounds of this invention are used as agriculturalfungicides, they can be applied to plant foliage, to seeds, to the soil,or to such parts of plants as the fruits themselves. Plants aresusceptible to a great many diseases which cause widespread damage; andamong some of the more important which can be mentioned are late blighton tomato, powdery mildew on cucumber (Frisiphe cichoracearum), cerealleaf rust on wheat (Puccinia rubigo-vera), and such common soil fungi asfusarium wilt (Fusarium oxysporum), the seed rot fungus (Phythiumdebaranum), and the sheath and culm blight (Rhizoctom'a solani). The newcompounds of this invention can also be employed as industrialfungicides to control a variety of fungi which attack such materials asadhesives, cork, paints, lacquers, leather, wood, plastics, and textilessuch as cotton and wool.

The quantity of active compound of this invention to be used for gooddisease control will depend on a variety of factors, such as theparticular disease involved, the intensity of the infestation,formulation, weather, type of crop and the like. Thus, while theapplication of only one or two ounces of active compound per acre of acrop may be sufficient to control a light infestation of certain fungi,a pound or more of active compound per acre may be required to control aheavy infestation of a hardy species of fungus.

The fungicidal utility of the compounds of this invention wasillustrated in an experiment carried out for the control of fusariumwilt (F usarium oxysporum). In this experiment soil was inoculated withthe fungus organism which was growing on wheat lima bean medium for 14days. The inoculated soil was placed in one ounce paper cups, and thesurface drenched with the test chemical, formulated as an aqueousemulsion of an acetone solution, at the indicated rates per four inchacre. After two to four days, the growth of the fungus was measured andrated in comparison with untreated controls. The results of thisexperiment are presented below:

Rate, lbs per Test Compound 4 inch acre Control l-( a-Thiocyanoacetyl100 100 indolene We claim:

1. A compound of the formula wherein X X X and X., are independentlyselected nitro or tertiary lower alkyl and at least two of X X from thegroup consisting of hydrogen, lower alkyl, X and X, are hydrogen.chlorine, bromine, trifluoromethyl, lower alkoxy and 2. The compound ofclaim 1, Z-(a-thiocyanoacetyl) nitro provided that only one of X X X andX is isoindoline.

1. A COMPOUND OF THE FORMULA
 2. The compound of claim 1, 2-( Alpha-thiocyanoacetyl) isoindoline.